Polymethylenepolyamine dipropionamides as environmentally safe inhibitors of the carbon corrosion of iron

ABSTRACT

Polymethylenepolyaminedipropionamides are carbonic corrosion inhibitors devoid of toxicity to the marine environment.

TECHNICAL FIELD

In the production of petroleum and gas, corrosion caused by carbon dioxide, which is known as carbonic corrosion, takes place at the bottom of wells, where the temperature is generally about 60° C. or more, in the surface pipelines and in refining of the crude oil. The approach usually adopted to overcome this is to use corrosion inhibitors based on amine salts, quaternary ammonium salts, imidazolines or phosphoric esters, but these compounds are not entirely satisfactory since they are ecotoxic in marine environments (acute toxicity to Skeletonema costatum at less than 1 ppm).

BACKGROUND ART

In European patent applications EP-A-520,761 and EP-A-526,251, it is mentioned that it is possible to reduce the toxicity of a diamine or of an imidazoline by reacting these molecules with acrylic acids; the larger the number of acrylic acid molecules, the more the toxicity reduces.

European patent EP-A-567,212 is based on the low toxicity of morpholine salts and phosphoric esters.

DISCLOSURE OF INVENTION

It has now been found that good inhibition of the carbonic corrosion of iron may be obtained with non-ecotoxic compounds of water-soluble polymethylenepolyaminodipropionamide type having a very low marine ecotoxicity (50 to 100 ppm on Skeletonema costatum), the general formula of which compounds is:

H₂NCO—(CH₂)₂—NH—[—(CH₂)n—NH—]m—(CH₂)₂—CONH₂

in which m is an integer which may take any value from 1 to 4, which represents the number of polymethyleneamino —(CH₂)_(n)—NH— chain units, it being possible for n to have, in each polymethyleneamino chain unit, an integer value from 2 to 6. This process for limiting the carbonic corrosion of steel in aqueous media forms the basis of the present invention, this process consisting in using, as non-ecotoxic corrosion inhibitor, an aqueous composition containing as active material at least one of the said polymethylenepolyaminodipropionamides, with the exception of tripropylenetetraaminedipropionamide. These compounds may be taken individually or as a mixture, and moreover the corresponding technical products are themselves mixtures of such individual compounds.

These polymethylenepolyaminodipropionamides are readily obtained by condensation of acrylamide with polymethylene-polyamine bases, for example the EDA, DETA, TETA, TEPA and HEPA bases in the ethyleneimine series, the PDA and DPTA (norspermidine) bases in the propyleneimine series, or hybrid compounds, for example of the spermine H₂N—(CH₂)₃—NH—(CH₂)₄—NH—(CH₂)₃—NH₂, or spermidine H₂N—(CH₂)₄—NH—(CH₂)₃—NH₂ type.

They are fully characterized by NMR spectrography (see Table I later).

These compounds may be used both in continuous injection and in a batchwise treatment. The useful doses are between 5 ppm and 20 ppm. They may be used directly or in the form of an aqueous or aqueous-alcoholic solution, preferably an aqueous-glycolic solution for flash-point reasons, containing from 20% to 65% by weight.

EXAMPLES

The examples which follow are intended to give a better understanding of the invention and its advantages.

Example 1

Preparation of Polymethylenepolyaminedipropionamides

The preparation of three molecules tested in Examples 2 and 3 below is described here.

Molecule A is the diamide H₂NCO—(CH₂)₂—NH—[—(CH₂)₂ —NH—]₂—(CH₂)₂—CONH₂ (RN 92009-86-4),

Molecule B is the diamide H₂NCO—(CH₂)₂—NH—[—(CH₂)₂ —NH—]₃—CH₂)₂—CONH₂,

Molecule C is the diamide H₂NCO—(CH₂)₂—NH—(CH₂)₃—NH—(CH₂)₂—NH—(CH₂)₃—NH—(CH₂)₂—CONH₂,

A, B and C are obtained by condensation of acrylamide with a polyamine, diethylenetriamine, triethylenetetraamine and bis(propylamino)ethylenediamine respectively, according to the following procedure.

Compounds Charged:

Acrylamide 2 mol

Polyamine 1 mol

Water 7% by weight of the total charge

Ethylene glycol 28% by weight of the total charge

Procedure:

Charge the amine, the water and the ethylene glycol into the reactor and heat to 60° C. under a stream of nitrogen.

At this temperature, introduce the acrylamide over about 2 hours.

Keep the mixture steady at 60° C. for 5 hours.

Monitor the reaction progress by ¹H/¹³C NMR.

Recover the polymethylenepolyaminedipropionamides directly in the form of solution.

The ¹H/¹³C NMR characteristics of products A, B and C will be found in Table I, in which (s) means singlet, (t) means triplet and (m) means multiplet.

TABLE I NMR spectral characteristics of compounds A, B and C (200 MHz ¹H spectrometer) Compound A 1 2 3 4 5 5 4 3 2 1 H2N CO CH2 CH2 NH CH2 CH2 NH CH2 CH2 NH CH2 CH2 CO NH2 M: 245.32 g.mol⁻¹; C₁₀H₂₃N₅O₂ Yield (%) = 97 ¹H NMR (D₂O): 2.34 (t, 4H, H₂); 2.58 (s, 8H, H₄ and H₅); 2.73 (t, 4H, H₃) ¹³C NMR (D₂O): 36.7 (C₂); 46.7 (C₃); 49.6 m, C₄ and C₅); 179.6 (C₁) Compound B 1 2 3 4 5 6 6 5 4 3 2 1 H2N CO CH2 CH2 NH CH2 CH2 NH CH2 CH2 NH CH2 CH2 NH CH2 CH2 CO NH2 M: 288.39 g.mol⁻¹; C₁₂H₂₈N₆O₂ Yield (%) = 94 ¹H NMR (D₂O): 2.34 (t, 4H, H₂); 2.58 (s, 12H, H₄ to H₆); 2.73 (t, 4H, H₃) ¹³C NMR (D₂O): 36.7 (C₂); 46.7 (C₃); 49.6 (m, C₄ to C₆); 179.6 (C₁) Compound C 1 2 3 4 5 6 7 7 6 5 4 3 2 1 H2N CO CH2 CH2 NH CH2 CH2 CH2 NH CH2 CH2 NH CH2 CH2 CH2 NH CH2 CH2 CO NH2 M: 316.45 g.mol⁻¹; C₁₄H₃₂N₆O₂ Yield (%) = 90 ¹H NMR (D₂O): 2.34 (t, 4H, H₂); 2.58 (s, 12H, H₄ to H₆); 2.73 (t, 4H, H₃) ¹³C NMR (D₂O): 30.5 (C₅); 36.9 (C₂); 46.7 (C₃) 48.7 (m, C₄ and C₆); 49.6 (C₇); 179.5 (C₁) Comments: In all cases, the coupling constant JH₂H₃ is 7 Hz

It is noted in passing that compound B H₂NCO—(CH₂)₂—NH—[—(CH₂)₂—NH—]₃(CH₂)₂—CONH₂ is a new product. It is also a subject of the present invention.

Example 2

The experimental procedures intended to evaluate the corrosion-inhibitory efficiencies in carbon dioxide-saturated medium of the products used (A, B and C of Example 1) are described in this example. In order to simulate the corrosive medium, a solution of NACE type containing 50 g/l of NaCl and 0.25 mg/l of acetic acid, saturated by continuously bubbling CO₂ through, depending on the case, and with inhibitor added or not added, is used.

Experimental Procedures

The process is performed in a thermostatically regulated 600 ml Pyrex cell including, besides a gas inlet and outlet, three electrodes coupled to the cell by ground joints, namely a carbon-steel working electrode whose surface of contact with the corrosive solution is 1 cm², a saturated calomel reference electrode and a platinum counterelectrode having a very large surface of contact with the corrosive solution. 500 ml of the corrosive solution is placed in the cell, as control or with inhibitor added, after which the counterelectrode and the reference electrode are put in place. The solution is de-aerated by bubbling nitrogen through for one hour and is then saturated with CO₂ by bubbling for at least one hour. In order to ensure good saturation with CO₂, this gas is left to bubble through throughout the experiment.

The rate of corrosion V_(corr) is measured by a method of measuring polarization resistance, which is known in the art. The corrosion rate reading is taken after stabilization for 6 hours.

The percentage of protection (%P) which allows the corrosion-inhibitory efficiency of the test product to be expressed is given by the relationship:

%P={(V⁰ _(corr)−V^(i) _(corr))/V⁰ _(corr)}×100

where V⁰ _(corr)=rate of corrosion without inhibitor

V^(i) _(corr)=rate of corrosion in the presence of a dose of inhibitor.

Table II collates the percentages of protection at room temperature (25° C.) as a function of the nature of the polymethylenepolyaminodipropionamides used and their dose.

TABLE II Carbonic corrosion-inhibitory efficiencies PERCENTAGE OF PROTECTION (%) Molecules/dose (ppm) 10 20 50 100 A 24 44 48 53 B 34 43 48 56 C 63 70 73 82

Example 3

The ecotoxicity measurements for various polymethylenepolyaminedipropionamides were carried out on a bacterium (Photobacterium phosphoreum) and on an alga (Skeletonema costatum) . The bacterial test is the Microtox test carried out according to AFNOR standard NF T90-320. The toxicities on Skeletonema costatum are determined according to the method ISO/DIS 10253. The Microtox toxicity is expressed as LC₅₀ (lethal concentration in mg/l to destroy 50% of the population in 15 minutes). On Skeletonema costatum, the toxicity is expressed as EC₅₀ (effective concentration in mg/l to inhibit the growth of 50% of the population in 72 hours).

Table III gives the toxicities obtained for compounds A, B and C.

TABLE III Skeletonema Microtox costatum (EC₅₀) in Toxicity (LC₅₀) in mg/l mg/l A 128 50 to 100 B 104 50 to 100 C 127 5-10 

What is claimed is:
 1. Process for limiting the carbonic corrosion of steel in aqueous media, wherein said process comprises adding to a steel containing aqueous media an aqueous composition comprising a non-ecotoxic corrosion inhibitor which is at least one of the polymethylenepolyaminedipropionamides compounds corresponding to the formula: H₂NCO—(CH)₂—NH—(—(CH₂)n—NH—)m—(CH₂)₂—CONH₂ in which m is an integer from 1 to 4, which represents the number of polymethyleneamino —(CH₂)n—NH— chain units, n having, in each polymethyleneamino chain unit, an integer value from 2 to 6, with the proviso that the polymethylenepolyaminedipropionamide compound is not tripropylenetetraamine dipropionamide.
 2. Process according to claim 1, wherein the molecule used is diethylenetriaminedipropionamide of formula: H₂NCO—(CH₂)₂—NH—(—(CH₂)₂—NH—)₂—(CH₂)₂—CONH₂.
 3. Process according to claim 1, wherein the molecule used is triethylenetetraaminedipropionamide of formula: H₂NCO—(CH₂)₂—NH—(—(CH₂)₂—NH—)₃—(CH₂)₂—CONH₂.
 4. Non-ecotoxic inhibitor of the carbonic corrosion of steel in aqueous media, consisting of an aqueous or aqueous-alcoholic solution containing 20-65% by weight of at least one compound corresponding to the formula: H₂NCO—(CH)₂—NH—(—(CH₂)n—NH—)m—(CH₂)₂—CONH₂ in which m is an integer from 1 to 4, n having, in each polymethyleneamino chain unit, an integer value from 2 to 6, with the proviso that the polymethylenepolyaminedipropionamide compound is not tripropylenetetraamine dipropionamide. 